Metalliferous azo-dyestuffs and process of making same



Patented Get. 27, 1931 UNITED STATES PATENT OFFICE;

a HANS GUBLER ANDGUILLAUME DE MON TIYIOLLIN, OE BASEL, JOSEPH SPIELER,OF LAUFEN, SWITZERLAND, ASSIGNORS'TO THE FIRM SOCIETY OF CHEMICALINDUSTRY IN BASLE, OF BASEL, SWITZERLAND MET ALLIFEROUS AZO-DYESTUFFSAND PROCESS OF MAKING SAME No Drawing. Appl ication fil ed IToveniber30, '1929} Serial No. 410,868, and in Switzerland December Thisinvention relates to the manufacture of new Inetalliferous azo-dystufissuitable for dyeing various fibers,.but particularly vegetable fibersand artificial fibers consisting of so-called regenerated cellulose. It

f comprises the processof making these dyestuifs, the dyestuffsthemselves, and the material dyed with these new 'dyestufisn Theinvention consists in producing complex metal compounds of azo-dyestuifsof the general formula V g I,

in which R is the residue of the diazotiz'ing component consisting ofthe sulionated nucleus of the benzene or naphthalene series, R is anunsulfonated nucleus of the benzene series which contains in ortho-position to the second azo-group an OH-group, one of these twosubstituents being in para-position to the first azo-group,R is theresidue of a coupling component which can couple once or several times,and a: is a whole number which isnot higher than thenumber of thepositions capable of coupling in the residue R These products are Ivaluable V dyestuffs capable of dyeing vegetable fibers orartificialfibers belonging to the group of regenerated cellulose, such'as viscoseor cupram- I monia, silk, or annual fibers, such'as wool,

leather, natural silk or loaded silk, violet, blue-green and grey tintswhich have very 7 good properties of fastness, particularly very good toexcellent 'fastness to light. They form dark powders which dissolve inwater to solutions having the above mentioned colors. 1 7

These metalliferous dyestuffs are made by treating the parentazo-dyestufi with an agent yielding metal capable of forming complexes,or a mixture of such agents, such as salts of copper, chromium, nickel,iron,

cobalt, titanium, aluminum, etc., or the corresponding oxides,hydroxides or salts, which these compounds form withalkalies or bases.

- Thenew metalliferous dyestuffs may alsobe made together withproduction .of the corresponding azo-dyestufis in a single operation bytreating a diazo-compound'of the general formula I in which R and R havethe aforesaid signification, with the coupling component designatedabove as R in presence of a metal yielding agent referred to above. 1

- Those dyestufi's of this group which have affinity for cotton can alsobe made in the dyebath or on the fiber by treating the corre- 'spondingazo-dyestufi' in the dye-bath oron lene-fi-sulfonic acid, an N-acidyl-,N-alkylor N-aryl-derivative of such an acid, includ- .7

ing obviously the corresponding urea-, thioureaanddinaphthyl-derivatives; also triazine-, quinazoline-,pyridazineandpyrimidine-derivatives of the said amino-naphthols or otheramino-naphthols, such as,

among others, 1: S-amino-naphthols, and, quite generally, thosedyestufi's in which w is a whole number greater than 1;

The following examples illustrate the invention, the parts being byWeight Eat-ample 1 I A disazo-dyestutf is prepared by diazotizing 30.3parts of 2-aminonaphthalenel:8- disulfonic acid, coupling withaminocresol (CH :OH:NH =1:4: 3) and further dia- I zotizing and couplingwith 2-phenylamino-5- hydroxynaphthalene-7'-sulfonic acid. The

'azo-dyestuff thus obtained of the formulais dissolved in 500 parts ofwater. The solution is heated to 50 C. and mixed with an ammoniacalsolution of 25 parts of crystallized copper sulfate. The temperature isi maintained for 1 hour at 50 C. and the copisialso' dyed blue tintsfast to light.

a zo-dy estuff of the'formulaj' per compound vvhich has been produced'isisolatedby saltingout and filtering. It dyes cotton blue tints. The bluetints produced on so-called stripeycviscose-silk are very equal-andveryfast tolight. LNatural silk L scfparts or the so -stem thetetrelgi Imade ecidw with 2racetylamino l hydroxyhenzene, sa

' ponifyi'ng further diazotizing andfcoupling.

(and the solution is wholeisistir'red for 2 hoursnt 75-9596. The

3 separated. coppersalt is. filtered, dissolved in Initial component(contains Middle component (contains the Endcomponent (contains the Tintoia mctalcompound,

' V {the residue R1) 7 1 resldue Ra) V residue Ra) l} on the fiber I.Sulfanilic acid Aminocresol. CHzzOHzNHg=1z 2{phenylamino-5 hydroxyneph-Guecompound' greenish blue 7 l 4:3 h thalene-Hulfonic acid I V (cottonorviscose silk) II, Metemhc ac1d Ammocresol OHmOHrNH i:2-iphenylamino-s-hydroxynephe Oil-compound blue (cotton or f r Vthalene-Fsulionic acid I viscose silk) V I IIL Metamlic acid Ammocresol.CH3:OH:NH=1: 2'-phenylamin0-S-hydroxynaph- Ou-oompoundidark grey (cotle thelene-6-sulfonic' acid V ten or viscose silk), j IY. Metsnilic acidAmmocrcsol CH3: OH:NH2=1: 128 -amino hydroxynaphthalener Gil-compoundgreen-bluev (cot- 1 I .453 I 3:6-disulfonie acid tan or viscose silk) 2naphthylspine-4:8,- Aminocresol CH3: O,H:NHg=l: 2- phenylemino-5-l1ydroxynaph- Oil-compound, blue '(cotton' or V V d aC1d 3 r vthalenc-7-sulfonic acid viscose silk)- V Z-naphthyl-smmeAgS -;AmmocresolOH3:OH:NH2=1: Z-phenylemino -5'-.hydroxynaph- (Jr-compound blue 'green(cotdisulfonicecid .423 V thalene-7-sulfonic acid' toner viscosejsilk)VII. 2- napl1thyl smlne 4:8 Ammocresol OH'agOHcNHFl: 1:8-emino-hydroxynaphthalenc- (Du-compound green (cotton or disulfonic ac d 1y4:3, I V l-sulfonic acid I r viscose silk) VIII; 2 naphthyl q 116 41 8 1Ammo res l CHs=1G N-Hz,=' l: Semino hvdroxynaphthalene Gmc'ompound green(cotton or disulfonic geld .v e 4:3 3:6-disulfonic acid V viscose silk)7 IX. Sulfanil c ecidm. 0rtho-am n0'nh nol Urea of2-amino-5-hydroxy-naph- (Eu-compound brownish red I Sulfan l c ac d;Ortho amin0-phenol" thalene-7-sulfonic acid (cotton'or viscose silk) 7X,Sulfan l c ac d Ortho-ammo-phenoL- 2:2 -dinaphthylemine-5z5 -dihy-(Eu-compound intense red blue 7 & l l P 'D 'droxy-7: 7-disulfonic acid J'(cotton or viscose silk) X sll a gla i V -phenoln 2-ph enylaminos-hydroxynaph Gil-compound red blue (cotton V I .7 j thalene 7-su1fonicacid 'or viscose silk) XII. slllfanlllcafild Ag gnocresol CHsZOHtNHg3-methyl-5-pyraz0lone; Cr-conipouzid violet(onwcol)' XIII; Sulfanilicamdg glofite CHQ 'NH2 I: Barbituric'acidn' (Jr-compound violet (on Wool)The o m o the dyest fl IV 15 l s1st1ng;ot agents y eldlng copper andchrov an'excessofammonio-solutionof 3. perfcent.

strength at. 60 9 G. and then the ammonium salt of; the copper complexis separated and isolated "by. ,precipitatiouby' means of. com- Inonagltlalt dyes :cotton directly brownish, reel-v olettiilts ofnexcellentiastness to light.

The following tables'hovizsl the constitution of and tints producedbysome dyestufis made hy-this inventiom f '1 c 1 I What we claim is:-

dyestu flis suitable-for dyeing vegetable filoers artificitil-fibersandanimal fibers, by treetingi vvithj og entsdyielding metals capable "ofthe; ezodye'stfitsffof the R ois an unsulfonated nucleus of thehenzeneEll series which contains in ortho-position to the I two substituentsbeing" infpara 'p'osition to second azo group yan OH-groupllone of thesethe first'aZo-gronp; Rg is-the'residue of a coupling component whichcagn couple once up to threetime's, andfm is a ivhole number Which isnot higher than three, i r 2.; A manufacture of metztlliferousazodyestuffs suitable for dyeing vegetable fibers, artificial filoersandanimal fibers, by treating .with 2t group of agents yieldingmetalsconsour no *NH; f

miu n on'azo-dye'stuff of the general formula H I in is: the residue ofa pdiazoiu'zing 1 component consisting of a sulii'oneted nucleus times,and w is a whole number v stufi's for'dyeing vegetable fibers,artificial fibers and animal fibers, by treating with agents yieldingcopper an azo-dyestuff of the general formula in which R is the residueof a diazotizing component consisting of a sulfonated nucleus of thebenzene or naphthalene series, R is an unsulfonated nucleus of thebenzene series which contains in ortho-position to the second azo-groupan OH-group, one of these two.

substituents being in para position to the first azo-group, R is theresidue of a coupling component which can couple once up to three times,and w is a whole number which is not higher than two.v

' 4. A manufacture of cupriferous azo-dyestuffs for dyeing vegetablefibers, artificial fibers and animal fibers,'by treating with agentsyielding copper an azo-dyestuff of the general formula benzene or nahthalene series R is an un- P sulfonated nucleus of the benzene serieswhich contains in ortho-position to the second azogroup an OH-group, oneof these two substitazo-dye'stuff of the formula agents yielding copper,and in an alkaline 4 uents being in para-position to the first azogroup,and R is the residue of a coupling component WlllCll can couple once ortwice.

5. A manufacture of blue to blue-green dyeing cupriferous' azo-dyestufisfor vegetable fibers, artificial fibers and animal fibers, by treatingwith agents yielding copper an N H-aryl Ha in which R is a sulfonatednucleus of the benzene or naphthalene series. I

6. The process of claim .4 for the production of cupriferousazo-dyestuffssuitable for the dyeingof vegetable, artificial and animalfibers, consisting in coupling, in presence of medium, thediazo-compounds of the general formula R N=NR N=NOH in which R is theresidue of a diazotizing component consisting of a sulfonated nucleus ofthe benzene or naphthalene series, and R is an unsulfonated nucleus ofthe benzene series which contains in ortho-position to the idiazo-groupan OH-group, one of these two substituents being in para-position to theazo-group, with compounds of the general formula HOaS- NHR in which Rmeans H, aryl or acidyl.

7 As new products of manufacture the complex metal compounds ofazo-dyestufis 0f the general formula i in which R is the residue of adiazotizing component consisting of a sulfonated nucleus of thebenzeneor naphthalene series, R is an unsulfonated nucleus of thebenzene series which contains in ortho-position to the second azo-groupan OH-group, oneof these two substituents being in ,para-position to thefirst azo-group, R is the residue of a coupling component which cancouple once up to three times, and a; is a whole number which is nothigher than three, which products, forming dark powders, are valuabledyestuffs capable of dyeing vegetable fibers and artificial fibersbelonging to the group of regenerated cellulose, and animal fibersviolet, blue, green and grey tints, which are fast tolight, anddissolving in water to solutions of similar coloration.

8. Asrnew products of manufacture the complex metal compounds derivingfrom a group of metals consisting of copper and chromium and from theazo-dyestufi's of the general formula in which R is the residue of adiazotizing component consisting of a sulfonated nucleus of the benzeneor naphthalene'series, R is an unsulfonated nucleus of the benzeneseries which contains in ortho-position to the second azo-group' anOH-group, one of these two substituents being in para-position to thefirst azo-group, R is the residue of a coupling component which cancouple once up to three times, and w is a whole number which is nothigher than three, which products, forming dark powders are valuabledyestuifs'capable of dyeing vegetable fibers and artificial fibersbelonging'to the group of regenerated cellulose, and animal fibersviolet, blue, green and grey tints, which arefast to light, and dissolving in water tosolutionsof similar coloration.

9. As new products of manufacture the complex copper compounds of theazo-dyestuffs of the general formula Rgjis an unsulfonatecl nucleus ofthe benzene *series which contains in ortho-positionto the secondazo-gr'oup'an-lOH-group, one ofthese twosubstituents beinginpara-position to a the first azo-group, R- fis'the residue of a. vCoupling component whichoancouple once or i u twice, and. mis awholenulnber'whiohisnot; higher than two, which products are valuj abledyestuffs c pable of dyeing vegetable fibers and-'artifioial fibersbelonging to the group of regenerated cellulose, and animal;

. fibers, violet, blue, green bIu e and grey tints 7 which arei'fast-to'light,*ancl dissolving in ,e water to solutions of similarcolorzttions.

: 1( ).*'As 'new products ofinenufeoture the I Complex'c'oppercornpounds" of the azo-dye fjst fii or the generalformula Isulfonatetl 'nuoleus' of the benzene series JR 1/i{=NL-RZN=NRQ in whichR liisf asulfonetted; nucleus of the benzeneflor naphthalene series, :3is an unwhich contains in-xortho -positioii to the sec-' on ti azo-groupan. -'OH-gr0i1.p', one of these two? substitu'ents "loeing inpara-position to 5 the first azo-gro'up, and R5 is the residue'of a,coupling component which oancouple" once or twice, which "products arevaluable dyestuffseapable of dyeing Vegetablefibers and "artificialfibersibelonging to the group of regeneretetl' eelluloseyand. eniinal;fibers, vi-

' olet, blue, green-blueand grejr tints which 7 l are fast to light,end; 'clissolving in water to solutions ofsimiler colorations; i

'11, As new products "of manufe'oture the Complex pp mpounds of theazo-dye V v stuifs ofthe general formula r L V {a "sulfoneted nucleusof-the benzene of naphthalene s'erlies,,which proding vegetable fibersand artificial fibers befwhi'ch' are fast to light, and. dissolving inwater to solutions of similar colorations,

longing to the group of regenerated cellulose, and animal fibers, blueand green-blue tints it I; In witness whereof we have hereunto signedourneines 18th day of November:

" HANS GUBLER

